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Issue 10, 2005
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The synthesis and characterisation of 4,1,2-MC2B10 metallacarboranes

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Abstract

Reduction of the tethered carborane 1,2-(CH2)3-1,2-closo-C2B10H10 followed by treatment with CoCl2/NaCp, [(p-cymene)RuCl2]2 (p-cymene = C6H4MeiPr-1,4), (PMe2Ph)2PtCl2 or (dppe)NiCl2 (dppe = Ph2PCH2CH2PPh2) affords reasonable yields of the new 13-vertex metallacarboranes 1,2-(CH2)3-4-Cp-4,1,2-closo-CoC2B10H10 (1), 1,2-(CH2)3-4-(p-cymene)-4,1,2-closo-RuC2B10H10 (2), 1,2-(CH2)3-4,4-(PMe2Ph)2-4,1,2-closo-PtC2B10H10 (3) and 1,2-(CH2)3-4,4-(dppe)-4,1,2-closo-NiC2B10H10 (4), respectively. All compounds were characterised spectroscopically and crystallographically. The cobalt and ruthenium species 1 and 2 have Cs symmetry in both solution and the solid state, having henicosahedral cage structures featuring a trapezoidal C1C2B9B5 face. The platinum and nickel compounds 3 and 4 have asymmetric docosahedral cage structures in the crystal (the more so for 4 than for 3) although both appear, by 11B and 31P NMR spectroscopy, to have Cs symmetry in solution. Low-temperature experiments on the more soluble platinacarborane could not freeze out the diamond–trapezium–diamond fluctional process that we assume is operating in solution, and we therefore conclude that this process has a relatively low activation barrier, probably <35 kJ mol−1.

Graphical abstract: The synthesis and characterisation of 4,1,2-MC2B10 metallacarboranes

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Publication details

The article was received on 04 Mar 2005, accepted on 22 Mar 2005 and first published on 14 Apr 2005


Article type: Paper
DOI: 10.1039/B503214H
Citation: Dalton Trans., 2005,0, 1842-1846
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    The synthesis and characterisation of 4,1,2-MC2B10 metallacarboranes

    R. McIntosh, D. Ellis, J. Gil-Lostes, K. J. Dalby, G. M. Rosair and A. J. Welch, Dalton Trans., 2005, 0, 1842
    DOI: 10.1039/B503214H

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